CN105874610B - photovoltaic cell - Google Patents

photovoltaic cell Download PDF

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CN105874610B
CN105874610B CN201480072139.5A CN201480072139A CN105874610B CN 105874610 B CN105874610 B CN 105874610B CN 201480072139 A CN201480072139 A CN 201480072139A CN 105874610 B CN105874610 B CN 105874610B
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electrode
semiconductor
semiconductor element
photovoltaic cell
bias
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CN105874610A (en
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科里·E·勒纳
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Columbus Photovoltaics LLC
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Columbus Photovoltaics LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/065—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the graded gap type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/07—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the Schottky type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Photovoltaic Devices (AREA)

Abstract

One kind includes semiconductor element（10）Photovoltaic cell, the semiconductor element is all made of single conduction type.The work function the having bias medium different from the work function of semiconductor element（26）, the bias medium（26）One face of cladding element, and band is caused to be bent, to generate electric field in space loading area.Electrode is contacted with the semiconductor element in space loading area.Carrier that light generates is absorbed by electric field acceleration towards electrode by semiconductor element.

Description

Photovoltaic cell
Cross reference to related applications
This application claims in the NO.61/899400 submitted on the 4th of September in 2013, the high band gap sun of entitled no semiconductor junction The equity of the applying date of the U.S. Provisional Patent Application of energy battery, the patent application are fully incorporated by reference herein.
Background technology
The present invention relates to photovoltaic cells.So far, people have put into sizable effort in this field to develop photovoltaic Battery, for example, semiconductor device can convert light into as electric energy.In general, such battery includes multi-lager semiconductor material, it is described partly to lead Body material includes n-type semiconductor and p-type semiconductor, and wherein n-type semiconductor is main or most electric charge carriers are electronics, and p Most electric charge carriers of type semiconductor are hole.These layers limit p-n junction jointly.Electrode is provided in and the opposition two in knot The semi-conducting material of side is in contact.When separate one another, since different doping, p-type material and n-type material have different take Rice energy level.Fermi level is so that the energy level that the probability that the energy level is occupied by an electron is 50%.When p-type material and n-type material are in electricity The p-n junction in pond is bonded to each other, and mutual fermi level enters balance and forms space loading area.Space loading area carries near knot Be supplied with electric power field.When light impinges upon on semi-conducting material, the photon of entrance makes electronics be promoted to conduction band from the valence band of semiconductor, Increase so as to cause number of charge carriers purpose.Term " band gap " refers between the valence band of semi-conducting material and the conduction band of material Energy difference.
The speed that the electric field of space-charge region makes electric charge carrier pass through p-n junction is accelerated.Hole and electronics are to opposite side To movement.Electron transmission is to the first electrode contacted with n-type material, otherwise hole-transfer is electric to second contacted with p-type material Pole.This can generate potential difference between the electrodes, to generate useful, available electric energy in electrode.External circuit is connect with electrode Using the electric energy.
Available voltage difference or potential difference from this p-n junction battery are limited.The maximum exported from this battery Voltage is limited by the difference between the energy level of valence band in the energy level and p-type material of conduction band in n-type material.This species diversity is usually less than The band gap of semiconductor.Ideal photovoltaic cell is made of the material with broad-band gap, for example, about 1.7 electron-volts or more.It is wide Can carrying material effectively absorbing wavelength can be approximately less than 800 nanometers of light.This light is in the visible and ultraviolet part of spectrum, and structure The earth is hit at the substantial portion of solar energy.In addition, the battery being made of wide bandgap material can be made of low bandgap material Battery is used in combination.In such an arrangement, broad-band gap battery is arranged on before narrow band gap battery.Long wavelength light cannot be by Broad-band gap battery absorbs, and across to narrow band gap battery, light is absorbed there.
The p-n junction formed by silicon can be made up of relatively cheap technique, such as implant the dopants into silicon chip.So And silicon has 1.12 electron-volts of band gap.The manufacture of p-n junction battery in certain wide bandgap semiconductor materials, needs to pass through The order process of epitaxial deposition forms multiple layers.In epitaxial deposition process, by deposition materials, material is grown in substrate On, most typically from steam or gaseous state, in existing solid crystals so that growth Crystallization has crystal lattices The structure of spacing, the crystal lattices spacing are determined by the spacing of lattice of substrate.However, using certain wide bandgap semiconductor materials It is likely difficult to high quality semiconductor material of the growth with opposite conductivity type.Therefore, although being put into so far in this field To develop photovoltaic cell, further improve is still desirable for sizable effort.
Invention content
Photovoltaic cell according to an embodiment of the invention includes with the thickness direction between front, back side knead dough Semiconductor element.Semiconductor element is preferably all made of by n-type semiconductor or all p-type semiconductor.Bias medium preferably covers First face in the face of lid semiconductor element.The fermi level or work function that bias medium preferably has are different from semiconductor element The fermi level or work function of the standard of part.Bias medium causes the band in semiconductor element to be bent so that space loading area deposits It is in semiconductor element, and there are unidirectional potential gradient perforative space load zones in thickness direction.Battery is preferably also included in thickness The positive electrode and back electrode being spaced on degree direction, each electrode connect in space loading area with semiconductor element when there is no light It touches.
Another aspect of the present invention provides a kind of electricity-generating method.It is preferably included to keep single according to the method for this aspect of the present invention Run through the space loading area of semiconductor element in gradient direction to potential gradient, the semiconductor element is all by p-type semiconductor Or it is all made of n-type semiconductor.While this method is preferably also included in holding potential gradient, light is directed to space loadings Qu Zhong so that at least some light are by semiconductor absorber, and the light absorbed makes electronics be promoted to conduction band from valence band.This method is most preferably Further comprise the collected current in a pair of electrodes, a pair of electrodes be spaced in gradient direction and in space loading area or Proximity space load zones and semiconductor contact.Optimally, in collection step, electrode is in space loading region and semiconductor interface It touches.
Photovoltaic cell according to another aspect of the present invention is preferably included with the thickness between the first face, the second face knead dough The semi-conducting material in direction.Bias medium preferably only covers the first part in the first face, and causes the band in semiconductor element Bending.First electrode preferably covers and contacts the second part in the first face separated with first part.In this aspect of the invention, First electrode is not preferably contacted with bias medium direct conduction.Second electrode is preferably included according to the battery of this aspect of the present invention, Second electrode is contacted with semiconductor element at the position far from the first face.
Description of the drawings
Fig. 1 is the schematic cross-section for the photovoltaic cell being connect with external circuit according to one embodiment of the invention.
Fig. 2 and Fig. 3 is to describe battery cross sectional schematic diagram according to another embodiment of the present invention.
Fig. 4 is the cell plane schematic diagram described according to further embodiment of this invention.
Fig. 5 is the schematic cross-section along Fig. 4 center lines 5-5.
Fig. 6 is schematic cross-section similar with Fig. 5, but depicts the battery according to further embodiment of this invention.
Specific implementation mode
Photovoltaic cell according to an embodiment of the invention includes having to extend between front 12, the back side 14 and these faces The semiconductor element 10 of thickness direction.As used in this, and as usually understood in the art, the face of solid objects Between the shortest straight line of the thickness direction that extends between two sides direction.Two of which face is mutually parallel, such as Fig. 1 institutes Show, thickness direction is perpendicular to the direction in face.In the embodiment of description, thickness direction is the level indicated by arrow T in Fig. 1 Direction.Semiconductor element 10 selectively can be unified with one or more additional semiconductors or substrate layer 16,17 and 18.? In the present embodiment, extra play is separate to play a part of 10 region of the semiconductor body produced electricl energy, also, correspondingly, extra play Can be substantially any ingredient and any conduction type.For example, extra play may include electric insulation layer 17 and by having than element The layer 16 and layer 18 that the semiconductor of the smaller band gap of semiconductor in 10 is formed.Layer 16 and layer 18 can be opposite conductive-types Type, and conventional p-n junction battery with electrode therefore can be limited, the 21 and 23 of the electrode such as schematic diagram description.
In the present embodiment, semiconductor element 10 is all made of the semi-conducting material with single conduction type.Institute In the example of explanation, conduction type is N-shaped.Semiconductor can be substantially any semiconductor, for example, III-V semiconductors, are such as wrapped Include selected from by race that such as gallium, indium and aluminium form one or more group-III elements and selected from the race being made of nitrogen, phosphorus, arsenic and antimony One or more V group elements.Alternatively, semi-conducting material can be II-VI semiconductors, include selected from being made of cadmium, zinc and mercury One or more II races metal of race and one or more VI races element selected from the race being made of such as oxygen, sulphur, selenium and tellurium.Partly lead Body can also be IV races semiconductor, such as silicon or silicon carbide.Semiconductor may be undoped, it may be possible to a kind of or more by being added Intentional doping of the dopant to nominal semiconductor is planted, or may be to adulterate unintentionally, for example, passing through lattice vacancy.For example, gallium nitride It may be formed in the n-type semiconductor for being not intended to doping during common epitaxial growth.Its of dopant or semiconductor itself His details can be conventional.
In fig. 1 it is assumed that extra play 16,17 and 18 does not influence the electronic state of semiconductor.The attribute of material is not by the external world " standard " attribute for bothering referred to herein as material influenced.Material has conduction band and valence band.The standard energy level of conduction band is expressed For Ec, and the standard energy level of valence band is expressed as Ev.In the n-type semiconductor shown in, standard fermi level EFSLess than standard conduction band Energy level Ec。
The front surface 12 of the layer covering semiconductor element 10 of bias material 26.In this example, bias material 26 is as thin Layer, to make bias material to the light light transmission in wavelength, the light is by the light of semiconductor absorber.As the present invention is disclosed and is used Term " light transmission " indicates that element makes the essence part of the light in interested wavelength that will be transmitted by the element.Perfectly Light transmittance does not need to, for example, 100% transmission.Wherein, here, semiconductor element 10 is N-shaped, the mark that bias material 26 has Quasi-Fermi level EFMLess than the standard fermi level E of semiconductorFS.In other words, the work function Φ m of the bias material are more than and partly lead Work function of the body under its standard state.The work function of material is the energy needed for mobile electron to vacuum from fermi level. The work function of metal is also referred to as " electron affinity " of metal.In the particular example s hown, bias material 26 is conductive gold Belong to.For example, work as semiconductor element 10 for IIVI semiconductors, for example cadmium sulfide n is doped to 1017, there are about 4.2 electron-volts （"eV"）Work function, bias material 26 may be metal, such as with about 4.78eV work functions gold.In the present embodiment, Bias layer 26 is the sufficiently thin metal layer to light transmission.The metal is conductive, to which bias medium is as first electrode.
In Fig. 1, under dark condition, semiconductor element and dependency structure are shown in open circuit.With this condition, do not have Light is fallen in semiconductor, and no electric current flows through semiconductor.The work function of metal and semiconductor is balanced on an energy level, should Energy level is by common fermi level FEIt indicates.In the case of illustrated metal and semiconductor, balance fermi level FESubstantially The upper standard fermi level F equal to the metalM.In other words, the fermi level of semiconductor drops to balance fermi level FE.It is real Existing this point, electronics are transferred to bias medium from the adjacent front surface 12 of semiconductor.This makes semiconductor through semiconductor One region, which is referred to as " space loading area ", also referred to as " depletion region " herein, adjacent with front surface 12 to exhaust Electronics, therefore the zone positive charge, and make bias medium negatively charged.Charge in bias medium is concentrated in very thin Region in, which is usually several angstroms of thickness, is referred to as in " incremental charge area "（It is not shown）, abutted with semiconductor front surface 12. Electronics in the conduction band of the semiconductor adjacent with front surface is biased the repulsion of the negative electrical charge on medium.Gradually farther from positive Distance is gradually increased by the amount of the positive charge semiconductor between bias medium and electronics, repulsive force is made to reduce.In other words, There is electric field in the space loading area of semiconductor.In space loading area, any electronics in semiconductor conduction band has by electric field The additional potential of application, and therefore than the electron energy level higher of the conduction band outside space loading area.This is bent up by curve 20 Song indicates.Because the band gap of semiconductor is quantitative, the energy level of valence band also increases in space loading area, such as by the upward of curve 22 Bending indicates.Term is commonly used in the distortion of energy level in description space loading area " with bending ".The width that these curves are bent upwards Degree is equal to the difference between the standard fermi level and the standard fermi level of bias medium 26 of semiconductor 10.This species diversity is claimed " built-in voltage " for metal-semiconductor junction（"VBI"）.The intensity of electric field is indicated by the slope of curve 20, and in space loading The boundary in area gradually decreases to zero, as shown in the line 28 in Fig. 1.Under conditions of dark, open circuit, the thickness t in space loading areaSC Carrier concentration and built-in voltage V depending on semiconductorBIAnd dielectric constant.Thickness t under these conditionsSCIt can be quickly It is calculated by those skilled in the art.By way of example, for dense in different built-in voltage doped cadmium sulfide difference carriers Degree, tSCApproximation it is as shown in the table.Maximum field EMAXAlso it shows in tablei.
Table I
Cadmium sulfide n dopings 1013 1015 1017 1019
VBI 0.25 V
The thickness t in space loading areaSC 49000 A 4900 A 490 A 49 A
EMAX (V/cm) 1.0 x 103 1.0 x 104 1.0 x 105 1.0 x 106
VBI 0.5 V
The thickness t in space loading areaSC 70000 A 7000 A 700 A 70 A
EMAX (V/cm) 1.46 x 103 1.46 x 104 1.46 x 105 1.46 x 106
VBI 1.0
The thickness t in space loading areaSC 98000 A 9800 A 980 A 98 A
EMAX (V/cm) 2.0 x 103 2.0 x 104 2.0 x 105 2.0 x 106
Photovoltaic cell according to the present embodiment further includes second electrode 30.In thickness direction, second electrode 30 and front surface 12 is separate, and separate with first electrode 26.In other words, electrode 26 and electrode 30 do not contact each other, and between these electrodes There are non-zero distance d for thickness direction2.A part for semiconductor element 10 is set between these electrodes.In thickness direction, just The distance between surface 12 and second electrode 30 d2 are less than under dark, open-circuit condition, the thickness t in space loading areaSC.Change speech It, under dark, open-circuit condition, second electrode and the semiconductor contact in space loading area.Therefore, electrode 26 and electrode 30 be all It is contacted with the space loading area of semiconductor element 10.In the present embodiment, electrode 30 is to can be by being formed by layer 16 and layer 18 The lower energy photon light transmission of accessory unit.In practice, electrode 30 may include metal thin layer or it is multiple be spaced it is impermeable Optical conductor so that light can pass through the spatial transmission between conductor.In the embodiment in figure 1, second electrode 30 is assumed to be and half Conductor Ohmic contact.Therefore it is presumed that purpose be to illustrate that second electrode 30 does not cause apparent band bending, or it is otherwise bright Development rings the configuration of conduction band in space loading area.Such as it is appreciated that from inspection Fig. 1 in the thickness direction from knot 12 to second electrode With potential gradient, the knot 12 is between bias material 26 and semiconductor.In other words, the gradient direction in the present embodiment and thickness It is identical to spend direction.The circuit 29 schematically shown in Fig. 1, including 31 He of switch that can be connected between electrode 26 and electrode 30 Load 33.
In operation, light passes through light transmission bias material 26 and enters semiconductor.Light is positioned at front surface 12 and theoretical boundary It is absorbed in the region of semiconductor between 36.Luminous intensity I at the depth X apart from front surface 12XIt is provided by following equation：
IX=I0e-αX
Wherein：
IOIt is the luminous intensity at front surface 12；And
α is that light is irradiated on the semiconductor, the absorption coefficient of semiconductor.Unless otherwise noted in the disclosure, the value of α It should be taken as the average value of the part of solar radiation of the energy higher than semiconductor band gap.
As used in the disclosure, the thickness t of absorption regionAIt is taken as being equal to depth X equal to α-1.In this depth, IX/I0Equal to e-1Or about 0.37.In other words, tAFor about 63% absorbed depth X of incident photon.Thickness tAIt can be more than or less than The thickness t in space loading areaSC, but preferably, tALess than tSC.Again for example, cadmium sulfide provides about 4000 angstroms of thick uptake zones Domain.
The absorption enhancement electronics of the photon of light is from valence band to conduction band.This is indicated by the arrow 32 in Fig. 1.Therefore, the suction of light Receive the carrier concentration for increasing semiconductor.Photon energy is accelerated by potential gradient electric in space loading area, forms additional carry Stream.Therefore, electronics left from front surface and towards second electrode move, conversely, hole towards front surface 12, bias material and Electrode 26 moves.Electron transmission is to second electrode 30 so that second electrode is negatively charged relative to bias medium and first electrode 26 Lotus.Minority carrier（Hole is shown in n-type semiconductor）Number increase relative to the peanut under dark condition at present Minority carrier is especially notable.The accumulation of minority carrier tends to reduce the thickness in space loading area.This passes through the boundary in Fig. 1 28 ' schematically show.It is desirable that second electrode 30 is arranged in the thickness of space loading area reduction, as shown in Figure 1.For example, In the photovoltaic cell used for land, when battery is subjected to 1 solar irradiation, second electrode is preferably still in space loading area In thickness.As used in the disclosure, term " sun " refers to light, and the light is with 1000 watts every square metre of intensity and right It should be in the spectrum of the spectrum of the solar energy shock earth.This spectrum is referred to as AM1.5 spectrum.In the open circuit condition, with external circuit The size of no current flows in 30, interelectrode potential difference will be less than the band gap of semiconductor.When switch 31 is closed, electronics will be from Second electrode 30 flows through external circuit to first electrode, and in the case, bias material 26 will be combined with hole.In semiconductor Internal current is referred to as photoelectric current, and by the arrow I in Fig. 1PHOTOIt indicates.
Electric field in space loading area causes carrier, especially electronics, accelerates to relatively high speed.In addition, electric The spacing of pole being relatively close to, makes the distance minimization moved by carrier.This is even more important, wherein constituent element 10 Semiconductor be direct semiconductor, and photonic absorption processes be direct absorption process.As used in the disclosure, term is " straight Connect transition " refer to the process that photon is absorbed by the quantum leap of electronics, the quantum leap of the electronics be from valence band to conduction band, The process or need not generate other particles or wave with other particles or wave interaction.This direct transition process should with It connects transition process to compare, indirect transition process is usually directed to interact with " phonon ", for example, shaking in semi-conducting material Dynamic wave.Term " direct semiconductor " refers to absorb the semiconductor of photon in direct transition process.Because of direct transition Process pertains only to two particles or wave interaction, for example, photon and electronics, if hit energy that photon has at least equal to Band gap, absorption process may occur.Therefore, direct semiconductor plays very efficient absorbing material.However, reversed jump It moves, for example, electronics drops to valence band from conduction band, is referred to as " Carrier recombination ", it is also possible in direct semiconductor.Change speech It, the Carrier recombination in direct semiconductor occurs far faster than in indirect semiconductor.Because of carrier electricity shown in Fig. 1 It is fast moved in the opposite direction in the inter-electrode space in pond, and due to interelectrode apart from small, a large amount of carriers survivals are abundant Time is to reach electrode so that a large amount of electric currents can be generated by battery.
In contrast, in the conventional structure for being referred to as " Schottky diode ", second electrode outside space loading area very Remote position and semiconductor contact.The carrier caused by the photonic absorption will expand across the one big region of semiconductor It dissipates, it is not influenced by electric field associated with space loading area.Therefore, carrier is experienced by lasting long before reaching electrode Residence time.Such Schottky diode structure formed by direct semiconductor is attempted to be used as photovoltaic cell, it will be through By a large amount of Carrier recombination, and generate reduced output current.
The battery comprising semiconductor element 10 can be made of direct semiconductor as shown in Figure 1.In addition, the battery does not wrap Containing p-n junction.Therefore, this battery can be made of various semiconductors.For example, it is difficult to which manufactured p-type semiconductor can be made With.Certain semiconductors show N-shaped doping, even if not intentionally adding dopant.When use such semiconductor, what battery included Semiconductor 10 can be manufactured without any intentional doping.
The photon that the energy having is less than the band gap of semiconductor in element 10 passes through semiconductor without being absorbed, and across saturating Optoelectronic pole 30 and 21 so that they reach the additional photovoltaic cell being made of layer 16 and layer 18.The battery absorbs these photons simultaneously Potential is generated between electrode 21 and electrode 23.These electrodes can be connected to another external circuit of any configuration（It is not shown）.? In one example of such circuit, electrode associated with extra play 16 and extra play 18 and electrode associated with semiconductor 10 26 and electrode 30 connect.Therefore, which plays composite battery as a whole, as short wavelength light is including element 10 Front battery absorbed and be converted into electric energy, and as the long glistening light of waves is converted into the back side battery comprising layer 16 and layer 18 Electric energy.In a further embodiment, the balancing cell being made of layer 16 and layer 18 can be omitted, and second electrode 30 can be reflection Property.In such an arrangement, second electrode redirects any unabsorbed light, and light returns to first electrode and the second electricity In space between pole.The reflected light is by the photon of the band gap bigger for the energy ratio semiconductor element 10 having including some.When When the return of these photons is moved towards first electrode 26, will at least partly it be absorbed.In further modification, carry as shown in Figure 1 For a kind of balancing cell formed by layer 16 and layer 18, but second electrode 30 is formed selective reflecting structure.The structure is anti- It penetrates high-energy photon to return towards first electrode 26, but to lower energy photon light transmission.In the modification of the arrangement, back side battery may include Optoelectronic pole, and can be placed in after the battery of the back side by one or more balancing cells that low bandgap semiconductor is formed so that it is additional Battery absorbs the light of more small wavelength.In further modification, semiconductor body includes one or more before being located at element 10 A balancing cell, the balancing cell are made of the semiconductor with the material bigger band gap than element 10.
Photovoltaic cell according to another embodiment of the present invention（Fig. 2）Similar to the battery as described above with reference to figure 1.? In this case, however, entire semi-conducting material of the semiconductor element only by being arranged between first electrode and bias material 126 Layer and second electrode 130 are constituted.In the present embodiment, the thickness of semiconductor element integrally having is less than the mark in space loading area Quasi- thickness.Here again, two electrodes are all contacted with space loading area.In the present embodiment, second electrode 130 includes metal The thin layer 111 of layer 131 and high doping semiconductor material, the thin layer 111 are contacted with semiconductor element 110.Specific show what is shown In example, semiconductor 110 is again N-shaped, and layer 111 is commonly referred to as n+ layers.Layer 111 is identical conductivity type, i.e. N-shaped, is made For the rest part of semiconductor body 110, but with so high carrier concentration so that playing metalloid in some aspects Effect.Such layer can promote the conduction between semiconductor body 110 and the metal layer of second electrode 130.A large amount of electronics Reaching second electrode 130 helps the electronics in second electrode to keep high concentration.If electronics is sufficiently high in the concentration of second electrode, It may not be necessary by adulterating the n+ layers formed.
Photovoltaic cell according to still another embodiment of the invention（Fig. 3）Similar to Fig. 1 and Fig. 2, the difference is that partly leading Phosphor bodies 210 are all formed by p-type semiconductor.In this case, bias layer 226 by with fermi level be higher than semiconductor 210 and work function formed less than the material of semiconductor.Equally in the present embodiment, bias material is generated in the semiconductors with curved It is bent.Here again, the spacing of the thickness direction between bias material 226 and second electrode 230 or distance are less than space loading The thickness in area so that second electrode 230 is placed in space loading area.The operation of this battery and basic phase as described above Together, the difference is that the flow direction of electric current is opposite.
Battery according to still another embodiment of the invention is as shown in Figure 4 and Figure 5.The battery includes comprising multiple electrodes element 301 first electrode, the multiple electrode member 301 are covered in the first surface 312 of semiconductor element.One such element It is shown in Fig. 5.Single electrode element is conductively connected by wiring route 303 is shown schematically in Fig. 4 each other.Wiring route Preferably use up the thin of actual capabilities so that wiring route only covers the minimum desired zone of first surface 312.
Bias medium 326 also covers the first surface 312 of semiconductor element.The preferred covering first surface of bias medium 326 A big chunk.Referred to herein as " first part on the surface ".In contrast, electrode member 301 is preferred covers first Surface 312 second, smaller part.In other words, electrode member 301 is located at 312 biased medium of first surface and is not present Region.Each electrode member preferably includes one or more conductive layers, such as metal layer.In the specific embodiment shown in, Each electrode member 301 includes the first metal layer 305 and the second metal layer 307 contacted with first surface.In other modifications, Only there are one metal layers or more than two metal layers can also be used.Electrical insulator 309 surrounds each electrode member 301 so that Electrode member is not contacted with 326 direct conduction of bias medium, and thus first electrode is as a whole.Wiring route 303（Figure 4）Also it insulate with biased element.Bias medium 326 is preferably light transmission, but can be conductor or high doping semiconductor.For example, such as Fruit semiconductor 310 is N-shaped, and bias medium 326 may include the thin layer of p+ types semiconductor 327, and be optionally included with positioned at p Transition layer 329 between+type semiconductor 327 and semiconductor element, 329 defining surface 312 of transition layer is to improve these elements Lattice Matching.Bias medium does not form a part for the conducting path across battery, and is not one of semiconductor element 310 Point.Therefore, here again, the semiconductor element 310 between electrode is all made of n-type semiconductor.Pass through p+ media The bias of n-type semiconductor broad-band gap can generate a large amount of band bendings and big built-in voltage.This can mitigate any is drawn by transition layer The reduction of the built-in voltage risen.
Battery is described as being connected to external loading 331, such as ohmic load.In operation, light is transferred to semiconductor master Bias medium is passed through in vivo, such as the arrow h in Fig. 5γIt is shown.However, the region for the main body being aligned with electrode member 301 keeps big No light on body.Therefore, these regions will not have a carrier, and by with electric conductivity be far below the area that is aligned with bias medium The electric conductivity in domain.
In the region of the semiconductor separate with electrode member, the operation of battery is like embodiment discussed above.Therefore, By the I of arrow markPHOTOThe photoelectric current of expression flows on the thickness direction between second electrode 330 and first surface 312.It is false Such as when the carrier concentration of first surface 312 is sufficiently high, the photoelectric current of the cell area far from electrode member 301 also will be along It is flowed towards electrode member perpendicular to the direction of thickness direction on surface 312 so that photoelectric current will pass through electrode member, and wear External loading 331 is crossed, and returns to second electrode 330.
The voltage difference of load 331 occurs as the external bias between the electrode member 301 and second electrode of first electrode. This external bias tends to cancel out the effect with bending.In other words, the external voltage applied by load is offset to be applied by bias medium The electric field in space loading area added.For example, curve 320 schematically shows leading there is no semiconductor when external bias Band, conversely, curve 321 is schematically shown, there are conduction bands when external voltage.This effect reduces field driving carrier and passes through half Conductor, and therefore tend to reduce photoelectric current.In addition, external bias tends to generate the electric current opposite with photoelectric current, such as arrow in Fig. 5 IDARKIt is shown.Which reduce the net currents flowed in the battery.
However, since external bias is applied between electrode member 301 and second electrode 330, these effects will mainly be sent out It is born in the region for the main body being aligned with electrode member.These regions constitute a relatively small part of battery.Because partly leading These regions of body have low-down carrier concentration, I substantially free from illuminationDARKTo be less than has first electrode covering I on entire positive comparable batteryDARK.In addition, those of semiconductor of separate electrode member region will be in semiconductor The reduction of smaller dependent deviation is born in electric field.It should be believed that these factors improve battery as shown in Figure 4 and Figure 5 Performance.
Battery according to another embodiment of the present invention（Fig. 6）Include the semiconductor element 410 formed by indirect semiconductor, For example, silicon.The battery has the first electrode for including multiple electrodes element 401, and multiple electrodes element its is merely illustrated in Fig. 6 One of.Electrode member 401 is spaced on the first surface 412 of semiconductor element.The battery further includes bias medium 426 With similar to the insulator 409 above by reference to Fig. 4 and Fig. 5 discussion.In this battery, the phase between bias medium and semiconductor Interaction, which is formed under dark, open-circuit condition, has thickness tSCSpace loading area.Second electrode 430 be located at space loading area Outer semiconductor contact.In this battery, the distance between front surface 412 and second electrode 430 d2More than tSC.The spy It includes n-type semiconductor to determine example.In region between the boundary 428 and second electrode 430 in space loading area, in dark condition Under no electric field.This is by the conduction band E that is schematically shown in Fig. 6CFlat part indicate.In operation, space loading area generates Electronics under the influence of space loading area internal electric field, towards boundary 428 transmit, then from boundary 428 to second electrode 430 expand It dissipates.Because semiconductor is indirect semiconductor, carrier will have enough service life to reach electrode.In this battery, it is combined The electronic component 401 at interval and the bias medium 426 to insulate with electrode member are provided and are similar to above by reference to Fig. 4 and Fig. 5 discussion Benefit.
Numerous modifications and the combination of element discussed above may be utilized.For example, the implementation discussed above by reference to Fig. 4-6 Example, electrode member are not necessarily the form of the circulating element of insulation as shown in the figure.In a kind of modification, electrode member is to put down each other The elongation strips that row extends, and be spaced on prolonging direction of the direction perpendicular to item.Including extending strip electrode element Arrangement in, connect up route 303（Fig. 4）It can be omitted.The metal layer of single electrode element can extend on the prolonging direction of item, And current-carrying is therefore can help to common conductor.The other structures of electrical connection single electrode element may be utilized.
In other embodiments, combination electrode can be formed by being described as the various electrodes of solid layer, and each includes one group The element being spaced.These elements can be lighttight, but the combination electrode as a whole will generally light transmission.? In another modification, light can be directed into battery, the back side of semiconductor element be passed through, as shown in Fig. 2 or Fig. 3.
In further modification, semiconductor element is formed a part for a larger semiconductor body, packet Include the extra play for the semiconductor for being covered in the first face of bias medium and semiconductor.Equally in this arrangement, bias dielectric overlay exists On one face of semiconductor element.
In embodiment discussed above, bias medium is in direct contact with semiconductor element.However, bias medium can pass through The thin layer for the insulator that conventional MIS knots use, separates from semiconductor element.For example, such insulating layer can be used for replacing Fig. 5 Shown in transition layer 329.It is this be arranged as it is less preferred because it reduces built-in voltage VBI。
Although the present invention refers to specific embodiment and describes herein, it should be understood that, these embodiments are merely illustrative Principles and applications.It should therefore be understood that many modifications can be carried out to illustrative embodiment, and other arrangements are not It is detached from the spirit and scope of the present invention being defined by the following claims.

Claims (19)

1. a kind of photovoltaic cell, including：
（a）Semiconductor element with thickness direction between the first face, the second face knead dough；
（b）Only cover and be in direct contact the light transmission bias medium of the first part in the first face, the standard Fermi that bias medium has Energy level is different from the standard fermi level of semiconductor, and wherein the bias medium causes the band in semiconductor element to be bent；
（c）First electrode, first electrode cover and are in direct contact the second part in the first face separated with first part, and first Electrode is not contacted with bias medium direct conduction, and the second part in the first face is smaller than the first part in the first face；And
（d）Second electrode, second electrode are contacted with semiconductor element at the position far from the first face, first electrode and the second electricity Pole forms connection so that photoelectric current flows through battery.
2. photovoltaic cell as described in claim 1, wherein semiconductor element have the between the first face and second electrode One region, and the wherein all p-types in first area or all N-shapeds.
3. photovoltaic cell as claimed in claim 2, wherein second electrode cover and contact the second face of semiconductor element extremely A few part.
4. photovoltaic cell as described in claim 1, wherein first electrode include on the first face of semiconductor element to each other Every multiple electrodes element, electrode member conductively connects to each other, and wherein bias medium extends between electrode member.
5. photovoltaic cell as claimed in claim 4, wherein each electrode member include the conductive material contacted with the first face and Conductive material from the insulating materials of bias dielectric separates.
6. photovoltaic cell as claimed in claim 4, wherein each electrode member includes light-proof material.
7. photovoltaic cell as described in claim 1, wherein second electrode and semiconductor element Ohmic contact.
It is partly led 8. photovoltaic cell as claimed in claim 7, wherein second electrode include contacted with semiconductor element highly doped Body layer and the metal contacted with heavily doped semiconductor layer.
9. photovoltaic cell as described in claim 1, wherein bias medium include the gold contacted with the first face of semiconductor element Belong to.
10. photovoltaic cell as described in claim 1, wherein bias medium include the highly doped of the first face of covering semiconductor element Semiconductor layer.
11. photovoltaic cell as described in claim 1, wherein semiconductor element are n-type semiconductor, and the expense that bias medium has Rice energy level is less than the standard fermi level of semiconductor element.
12. photovoltaic cell as claimed in claim 11, wherein semiconductor element are selected from by III-V semiconductors, II-VI semiconductors With IV races semiconductor group at race.
13. a kind of circuit including photovoltaic cell as described in claim 1 and a kind of being electrically connected to the first of photovoltaic cell The load of electrode and second electrode.
14. a kind of electricity-generating method, includes the following steps：
（a）First part and the bias physical contact between media of the first surface of semiconductor are kept, while also keeping first surface Second part is in direct contact with first electrode, and first electrode is kept not contacted with bias medium direct conduction, wherein described inclined The standard fermi level that pressure medium has is different from the standard fermi level of semiconductor, and bias medium causes in semiconductor element Band bending；And
（b）In step（a）In, keep second electrode to be contacted at the position far from first surface with semiconductor；
（c）In step（a）And step（b）In, light is directed in semiconductor so that at least some light by semiconductor absorber, and The light of absorption makes electronics be promoted to conduction band from valence band；And
（d）The electric current generated is collected in electrode.
15. method as claimed in claim 14 further includes the load between directing current through electrode, while bias being kept to be situated between Matter is electrically insulated with load.
16. method as claimed in claim 14 further includes stopping that light transmission enters the area for contacting the semiconductor being aligned with first The step of domain.
17. the method described in claim 16, wherein first electrode are lighttight, and stop step first electrode extremely A few part carries out.
18. method as claimed in claim 14, wherein semiconductor absorb light in direct transition process.
19. method as claimed in claim 14, wherein semiconductor absorb light during indirect transition.
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